CN104005072B - Method for sealing aluminum-alloy surface anode oxide film hole by adopting titanium dioxide gel - Google Patents
Method for sealing aluminum-alloy surface anode oxide film hole by adopting titanium dioxide gel Download PDFInfo
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Abstract
The invention discloses a method for sealing an aluminum-alloy surface anode oxide film hole by adopting titanium dioxide gel. The method comprises the following steps: carrying out anode oxidization, electrolytic coloring, and nanometer titanium dioxide gel hole sealing onto an aluminum-alloy matrix material, wherein an oxide film with a compact layer and porous layer structure is generated on the surface of the matrix material, so that corrosion resistance of the matrix material is improved; electrolytic coloring is used for depositing nano-metal antibacterial particles in the porous layer, so that the porous layer has an antibacterial performance; the titanium dioxide gel hole sealing is used for enabling nano titanium dioxide with self-cleaning and sterilizing effects to be stably exist on the aluminum-alloy surface, so that the aluminum-alloy surface has self-cleaning performances, and the aluminum alloy has dual antibacterial performances by virtue of the nano titanium dioxide and nano-metal antibacterial particles; meanwhile, the aluminum alloy also has a decorative effect. A multifunctional coating prepared by the method disclosed by the invention has various functions such as decoration, corrosion resistance, wiping resistance, antibacterial performance and self-cleaning performance, and can be used for aluminum-alloy preparation industries of food, medical treatment, tobaccos and the like. Besides, range of application of the aluminum alloy can be effectively expanded.
Description
Technical field
The invention discloses a kind of method in closing positive pole oxidation film on aluminum alloy surface hole, particularly relates to one kind and adopts dioxy
The method for changing titanium gel closing positive pole oxidation film on aluminum alloy surface hole.Belong to technical field of surface.
Technical background
Aluminium alloy density is low, but intensity is higher, and near or above high-quality steel, plasticity is good, is most widely used in industry
A class non-ferrous metal structural material, with excellent electric conductivity, heat conductivity and corrosion stability, industrially widely use, usage amount
Steel is only second to, is used in a large number in Aeronautics and Astronautics, automobile, machine-building, ship and chemical industry.Due to aluminium alloy light weight, valency
Honest and clean, toxicity is minimum, compares rustless steel and titanium alloy, and aluminium alloy is in the applications such as medical science, food, tobacco machine or home appliances
Price advantage is it will be apparent that therefore these aspects still have very big development space.
Aluminum is the active metal of comparison, and normal potential is -1.66V (vs.S.H.E), therefore aluminium alloy also can in atmosphere
The natural oxidizing layer for generating one layer of 0.01-0.1 micron, but this layer of oxide-film are oxidized than relatively thin, wearability, corrosion resistance etc. are
It is unstable, so being surface-treated to aluminium alloy, its wear-resisting, decay resistance etc. can be significantly improved.
Aluminium alloy can generate inner compact layer layer, the oxide-film of the special construction of outer layer porous layer Jing after anodic oxidation, this
Oxide-film has very high porosity and absorbability, and easily contaminated and corrosive medium corrodes, particularly aggressivity anion
(such as Cl-, S2-, cation) and hydrone etc. remain able to pass through oxide-film, (particularly aperture is rotten to cause corrosion resistance
Erosion) and wearability variation, it is therefore necessary to carry out sealing pores to improve its corrosion resistance.
The Application No. that inventor applies in June, 2012：" 201210212975.1 " are entitled：A kind of " medical science external
The electrochemical preparation method of aluminium alloy multifunction coating " patent of invention；By aluminum alloy base material is carried out anodized and
Electrolytic coloring, enables aluminum alloy to surface and forms porous oxide film and in fenestra containing metals such as certain silver, copper, zinc, finally, leads to
The mode for crossing decocting in water is sealed using the boiling water containing titanium dioxide nanoparticle to the porous oxidation fenestra that aluminum alloy surface is formed
Close；Make in oxide-film top layer both containing possessing the metals such as sterilization, antiseptical silver, copper, zinc, while and containing possessing self-cleaning function
Nano titanium oxide, enables aluminum alloy to have decoration, anti-corrosion, sterilization and the function such as self-cleaning.Aluminium alloy is met in medical science external side
The requirements in face, have expanded range of application of the aluminium alloy in numerous areas such as medical devices.But aluminum prepared by said method is closed
, also there is following defect in golden multi-functional coatings：
1st, because sealing of hole is using the boiling water sealing hole containing titanium dioxide nanoparticle, although boiling water sealing hole can be made using diffusion
It is diffused into during sealing of hole in oxidation fenestra, but by spreading the dioxy for being embedded into sealing of hole layer with part TiO 2 particles are made
Change the limited amount of titanium granule, photodissociation and automatical cleaning ability be not high；
2nd, due to combining between titanium dioxide granule and film layer, therefore, can be only present in fenestra, and can not adhere to
On oxide-film surface, that is to say, that the porous oxide film after being processed using boiling water sealing hole containing titanium dioxide nanoparticle, only at it
There is titanium dioxide granule in fenestra, film surface there is no titanium dioxide, further limit its photodissociation and automatically cleaning energy
Power.
3rd, after due to anodized and electrolytic coloring, the porous oxide film formed in aluminum alloy surface is mainly vigorous nurse
Body (aluminum oxyhydroxide), the resistance to strong acid of vigorous nurse body itself, alkali corrosion are poor, cause using after titanium dioxide granule boiling water sealing hole
Oxidation film layer is corroded rapidly, causes aluminum alloy surface color and luster aesthetics to decline rapidly, and wearability, corrosion resistance are reduced.
4th, boiling water sealing hole is adopted, observable index is higher.
With regard to titania gel as Process on Aluminum Alloy Oxidation Film sealing material, open report is not also seen so far.
The content of the invention
It is an object of the invention to provide a kind of employing titania gel closing positive pole oxidation film on aluminum alloy surface hole
Method, the inventive method process is simple is easy to operate, and pore closure rate is high, and hole sealing coating is well combined with matrix, with preferable
Mechanical property, effectively improve anti-corrosion, the wearability of aluminium alloy, meanwhile, enable aluminum alloy to surface possess sterilization, it is antibacterial, self-cleaning, dress
The several functions such as decorations.
The present invention is achieved by the following technical solutions：
The method that the present invention closes positive pole oxidation film on aluminum alloy surface hole using titania gel, comprises the steps：
The first step：Aluminum alloy surface electrolytic anodization
Using the one kind in aluminium alloy, graphite, rustless steel, lead, titanium alloy as negative electrode, closed with the aluminum for needing surface oxidation to protect
Gold carries out anodic oxidation as anode, and in aluminum alloy surface porous oxide film is formed；
Anode oxidation process is：
Anodic oxidation electrolyte is made up of sulphuric acid, aluminium ion, vitriolated quality volume in every liter of anodic oxidation electrolyte
Concentration is 120-180g/L, and it is 5-20g/L that aluminum ions mass-volume concentration is contained in every liter of anodic oxidation electrolyte；The aluminum from
The one kind of son in aluminum sulfate, meta-aluminate, aluminium hydroxide；
Oxidation current density is 40-60mA/cm2；
Second step：Surface-sealing
After the oxidized aluminum alloy coloring film surface water that the first step is obtained is rinsed well, it is placed in titania gel and soaks
Bubble 20-50min, takes out in 80-98 DEG C of drying；Titania gel sealing of hole film layer is obtained in aluminum alloy surface.
The method that the present invention closes positive pole oxidation film on aluminum alloy surface hole using titania gel, closes in first step aluminum
After gold surface electrolytic oxidation, electrochemical coloring is carried out to aluminum alloy surface, then, carry out surface-sealing.
The method that the present invention closes positive pole oxidation film on aluminum alloy surface hole using titania gel, aluminum alloy surface is carried out
The technological parameter of electrochemical coloring is：
With graphite as anode, with the aluminium alloy after anodic oxidation as negative electrode, electrolysis temperature is 40-80 DEG C, and electric current is close
Spend for 5-100mA/cm2, in 0.5-2, electrolyte is made up of coloring agent, complexant, solvent, per liter for the pH value control of electrolyte
The mass-volume concentration containing coloring agent is 5-50g/L in solvent, and the mass-volume concentration containing complexant is 20-60g/L.
The method that the present invention closes positive pole oxidation film on aluminum alloy surface hole using titania gel, the complexant is selected from
In tartaric acid, citric acid, pyrophosphoric acid, ethylenediaminetetraacetic acid, tartrate, citrate, pyrophosphate, edetate
At least one；At least one of the coloring agent in argent, copper, the inorganic salt of zinc；The solvent is distilled water.
The method that the present invention closes positive pole oxidation film on aluminum alloy surface hole using titania gel, anodic oxidation electrolysis temperature
10-40 DEG C of degree, the electrolytic oxidation time is 20-40min.
The method that the present invention closes positive pole oxidation film on aluminum alloy surface hole using titania gel, the electricity of electrochemical coloring
The solution time is 30-300s.
The method that the present invention closes positive pole oxidation film on aluminum alloy surface hole using titania gel, titania gel system
It is for process：Butyl titanate is added in dehydrated alcohol, mix homogeneously obtains solution A；Separately take glacial acetic acid again to mix with ethanol
To B solution；Then A is poured slowly in B, is stirred, obtain titania gel.
The method that the present invention closes positive pole oxidation film on aluminum alloy surface hole using titania gel, solution A is by 5-30mL
Butyl titanate is added in the dehydrated alcohol of 10-100ml, and mix homogeneously is obtained；B solution is by 5-30ml glacial acetic acid and 10-100ml bodies
Product percentage concentration is that 95% ethanol is mixed to get；After A is poured slowly in B, 30min is stirred, obtain titania gel.
The method that the present invention closes positive pole oxidation film on aluminum alloy surface hole using titania gel, the anodic oxidation electricity
Solution technique adopts DC source with galvano-chemistry bepainting technique；The DC source is constant-voltage DC source or constant-current dc electricity
Source.
The present invention adopts titania gel sealing of hole, the chemical bond of titanium dioxide and oxidation film layer is realized, due to oxygen
It is in itself aluminium oxide structure to change film, and colloidal sol prepares titanium dioxide and can therewith form firm Ti-O-Al keys, this combination by
In forming chemical bond, thus is combined with oxide-film it is very good, sealing of hole gel and oxide-film itself with reference to very firm, can in case
Only because being cleaned multiple times when using, wiping surface color and being wiped free of.In addition, using titania gel sealing of hole, substituting conventional
Boiling water sealing hole, on the one hand, can be with saves energy and water resource, on the other hand, because titanium dioxide is close in titania gel
Degree is bigger than in boiling water, and the content of titanium dioxide is greatly improved, and its viscosity and seriality can allow titanium dioxide convenient
Enter into positive pole oxidation film on aluminum alloy surface bottom hole portion, inwall and aluminum alloy surface；Titanium dioxide can preferably be played
Characteristic.Make titanium dioxide sealing of hole film layer good with matrix associativity, corrosion resistance is improved compared with boiling water sealing hole, and with antibacterial self-cleaning
Energy；
In addition, the present invention generates the special construction of inner compact layer, outer layer porous layer in aluminum alloy surface electrolytic anodization
Oxide-film after, using galvano-chemistry bepainting technique, metallic of the deposition with bactericidal effect in oxide-film outer layer porous layer
Such as silver, copper, zinc, surface not only can be enabled aluminum alloy to different colors are presented, with excellent dicoration, meanwhile, can be significantly
Degree improve aluminium alloy resistance to wiping and decay resistance, particularly, using silver, copper, zinc bactericidal property, greatly improve aluminum
The sterilization of alloy surface, self-cleaning property.Because fenestra is Nano grade, by the way that Theoretical Calculation is every square centimeter deposition is probably needed
Metal there was only more than ten milligrams, therefore cost is very low, and the sterilizing function of nano-sized metal particles (such as nanometer silver) is to pass through
Nano metal particles are invaded in antibacterial body, hinder the synthesis of certain enzyme in antibacterial body to kill antibacterial, can be reused,
Bactericidal property will not be lost with access times, therefore deposit sterilization particle, be reached low cost and increase substantially sterilization, decoration
Effect.
The present invention is completed using DC source anodic oxidation and electrolytic coloring, process is simple, the step of heat-tinting one, and
Color technique can change with electrolysis time and different colors are presented, with excellent dicoration, and meanwhile it is environmental friendly nontoxic, and have
There are antibacterial, bactericidal property.Finally, using titania gel hole sealing technology, process is simple, substantial amounts of electric energy and water money have been saved
Source, and titanium dioxide can be made to be stable in the presence of aluminum alloy surface, enable aluminum alloy to the effect with self-cleaning and double-layer antimicrobial.
The present invention prepare golden yellow oxide-film tool color it is golden yellow full, good decorative property, at the same have antibacterial, antibacterial, from
Clean, decoration etc. is multi-functional.
The golden yellow oxide-film of colloidal sol sealing of hole is good with substrate combinating strength, is wiped using reagent paper, just opens at least more than 10,000 times
Begin to decolourize.The resistance to wiping of boiling water sealing hole oxide-film containing titanium dioxide nano-particle is 3000 times or so.
Golden yellow oxide-film freezing corrosion is good, and the corrosion rate in 5% sodium chloride solution is 10-6-10-7A/cm2。
Compared with alloy matrix aluminum (10-4A/cm2) improve the 2-3 order of magnitude.Boiling water sealing hole oxide-film containing titanium dioxide nano-particle is anti-corrosion
For 10-6A/cm2。
Golden yellow oxide-film alkali-resistant property is good, in the drop alkali-resistant property experiment of the sodium hydroxide of 150g/L, resists
Corrosion reaches 40min.Resistance to this alkaline etching of boiling water sealing hole oxide-film containing titanium dioxide nano-particle is 20min or so, and equal conditions
The anticorrosive time of lower Process on Aluminum Alloy Oxidation Film only has more than ten seconds.
Golden yellow oxidation membrane coat antibiotic property is strong, the experiment of steamed bread contact antibiotic property, will not go mouldy within least 5 days, 7 days
Below also will not go mouldy completely, with good antibiotic property.And the steamed bread of aluminium alloy matrix surface is long in 24h under equal ambient
It is mould.Suppression of the boiling water sealing hole oxide-film containing titanium dioxide nano-particle to mycete can reach 3 days.
Golden yellow oxidation membrane coat photodissociation self-cleaning property is strong, in the experiment of photodissociation methyl orange, decomposes after 60min under sunlight
Rate is more than 40-88%, there is good photodissociation self-cleaning property.Boiling water sealing hole oxide-film containing titanium dioxide nano-particle is to methyl
The photodissociation rate of orange can be up to more than 50%.
In sum, the aluminium alloy multifunction oxide-film after the present invention is processed not only has excellent associativity with matrix,
Also there is very excellent corrosion resistance, resistance to wiping, antibacterial, the multiple performance such as sterilization, decoration performance, film layer is durable in use, property
Can keep constant.The various performances of aluminium alloy can be greatly improved, is that the range of application for expanding aluminium alloy opens new application
Field, can enable aluminum alloy to meet the needs of medical devices etc., be applied to medical device (such as stretcher, handrail, bedstead, operational tool
Deng), daily utensil (such as kitchen utensils, hold food appliance), the field such as articles for babies；Can suppress when food is held
Growth of antibacterial etc., improves the standard of living of the people, opens up new aluminium alloy application market.
Specific embodiment
Embodiments of the invention are described below in detail, described embodiment is exemplary, are only used for explaining the present invention,
And be not construed as limiting the claims.Certainly, those skilled in the art may propose accordingly to repair according to scheme described below
Change or change, these modification or change should be included in the present invention include within the scope of.
Embodiment 1
The first step：After according to conventional aluminum alloys polishing rust-removal, washing, pickling degreasing, washing step, aluminium alloy is immersed
In the sulfuric acid solution of 180g/L, wherein the aluminum sulfate containing 10g/L, using needing the aluminium alloy of oxidation as anode, negative electrode is also
Aluminium alloy, reaction environment temperature is 20 DEG C, and using constant current source, electric current density is 40mA/cm2, oxidization time is 30min, is taken
The aluminium alloy gone out after oxidation is rinsed in the clear water of flowing, removes the electrolyte on oxide-film surface, and in aluminum alloy surface silver is obtained
The oxide-film of Lycoperdon polymorphum Vitt；
Second step：By the first step gained aluminium alloy as negative electrode, with graphite as anode, electrolyte be 10g/L silver nitrate,
5g/L magnesium sulfate and 10g/L sodium citrates, with nitre acid for adjusting pH to 0.5, the silver gray aluminium alloy after then the first step is aoxidized
Immersion carries out in the electrolytic solution electrolytic coloring, and cathode-current density is 60mA/cm2, flavous oxygen is obtained after sedimentation time 90s
Change film.Then take out golden yellow aluminium alloy to rinse in the clear water of flowing, remove the electrolyte of residual；
3rd step：Titania gel is configured first：20mL butyl titanates are first added the dehydrated alcohol of 70ml, mixing is equal
It is even to obtain solution A；8ml glacial acetic acid is separately taken again is mixed to get B solution with the ethanol that the mass-volume concentration of 35ml is 95%；Then
A is poured slowly in B, 30min is stirred rapidly, obtain titania gel.Then, the golden yellow aluminium alloy for second step being obtained
Soak in titania gel after 30min, take out, be dried in 90 DEG C of drying baker after 30min and be cooled to room temperature, use clear water
Rinse well, dry, you can obtain titania gel sealing of hole film layer.
Golden yellow oxide-film tool color manufactured in the present embodiment is golden yellow full, good decorative property, at the same have antibacterial, antibacterial,
Self-cleaning, decoration etc. is multi-functional.Wiped using reagent paper, more than 10000 times, just start to decolourize；Corruption in 5% sodium chloride solution
Erosion speed is 10-6-10-7A/cm2, compared with alloy matrix aluminum (10-4A/cm2) improve the 2-3 order of magnitude；In the sodium hydroxide of 150g/L
Drop alkali-resistant property experiment in, it is anticorrosive up to more than 30min, and under equal conditions Process on Aluminum Alloy Oxidation Film the anticorrosive time
Only several seconds；The antibiotic property of coating is strong, in the experiment of steamed bread contact antibiotic property, aluminium alloy matrix surface under equal ambient
Steamed bread mildew in 24h, and the aluminium alloy that the present invention is processed can adhere to more than 72h, and 120 hours also will not be completely mould
Become；In the experiment of photodissociation methyl orange, resolution ratio reaches 88% after 60min under sunlight, there is good photodissociation self-cleaning property.
Comparative example 1
The step of technique first and second and example 1 of aluminium alloy multifunction coating are obtained using boiling water sealing hole containing nano titanium oxide
Unanimously.Be respectively anodized aluminum alloy and Process on Aluminum Alloy Oxidation Film is carried out electrolytic coloring silver.3rd step hole-sealing technology is as follows,
Oxidation and the aluminium alloy after electrolytic coloring are immersed in 20 minutes in the boiling water containing nano titanium oxide, are then taken out, dried,
Obtain the boiling water sealing hole oxide-film containing nano-titania particle.
This comparative example prepare golden yellow oxide-film tool color it is golden yellow full, good decorative property, at the same have antibacterial, antibacterial,
Self-cleaning, decoration etc. is multi-functional.Wiped using reagent paper, more than 3000 times or so, just start to decolourize；In 5% sodium chloride solution
Corrosion rate 10-6A/cm2, compared with alloy matrix aluminum (10-4A/cm2) improve 2 orders of magnitude；In the sodium hydroxide of 150g/L
It is anticorrosive up to more than 20min in the experiment of drop alkali-resistant property, and the anticorrosive time of Process on Aluminum Alloy Oxidation Film is only under equal conditions
There are more than ten seconds；The antibiotic property of coating is strong, in the experiment of steamed bread contact antibiotic property, aluminium alloy matrix surface under equal ambient
Steamed bread mildew in 24h, and the aluminium alloy for containing the boiling water treating of nano-titania particle can adhere to 3 days；Photodissociation methyl orange
In experiment, resolution ratio reaches 50% or so after 60min under sunlight, there is preferable photodissociation self-cleaning property.
Compared with the sealing of hole example of comparative example 1 by embodiment 1 it is found that using the technique of titania gel sealing of hole
The decorative coating of full color can also be obtained, in anti-corrosion, resistance to wiping, sterilization and the aspect of performance such as self-cleaning compared with boiling water sealing hole
The performance of coating more preferably, is more suitable for the aspects such as medical science external.
Embodiment 2
The first step：After according to conventional aluminum alloys polishing rust-removal, washing, pickling degreasing, washing step, aluminium alloy is immersed
In the sulfuric acid solution of 100g/L, wherein the aluminum sulfate containing 10g/L, using needing the aluminium alloy of oxidation as anode, negative electrode is also
Aluminium alloy, reaction environment temperature is 20 DEG C, and using constant current source, electric current density is 60mA/cm2, oxidization time is 30min, is taken
The aluminium alloy gone out after oxidation is rinsed in the clear water of flowing, removes the electrolyte on oxide-film surface, and in aluminum alloy surface silver is obtained
The oxide-film of Lycoperdon polymorphum Vitt；
Second step：By the first step gained aluminium alloy as negative electrode, with graphite as anode, electrolyte be 50g/L silver nitrate,
5g/L magnesium sulfate and 50g/L sodium citrates, with nitre acid for adjusting pH to 0.5, the silver gray aluminium alloy after then the first step is aoxidized
Immersion carries out in the electrolytic solution electrolytic coloring, and cathode-current density is 60 mA/cm2, obtain flavous after sedimentation time 30s
Oxide-film.Then take out golden yellow aluminium alloy to rinse in the clear water of flowing, remove the electrolyte of residual；
3rd step：Titania gel is configured first：20mL butyl titanates are first added the dehydrated alcohol of 100ml, mixing
Uniformly obtain solution A；Ethanol of the 8ml glacial acetic acid with the 95% of 20ml is separately taken again is mixed to get B solution；Then A is poured slowly into into B
In, 30min is stirred rapidly, obtain titania gel.Then, the golden yellow aluminium alloy that second step is obtained is immersed in into titanium dioxide
40min in titanium gel, in 98 DEG C of drying baker 30min is dried, and further takes out to cool down and rinsed well with clear water, drying, i.e.,
Titania gel sealing of hole film layer is obtained.
Golden yellow oxide-film tool color manufactured in the present embodiment is golden yellow full, good decorative property, at the same have antibacterial, antibacterial,
Self-cleaning, decoration etc. is multi-functional.Wiped using reagent paper, more than 4000 times, just start to decolourize；Corruption in 5% sodium chloride solution
Erosion speed is 10-5-10-6A/cm2, compared with alloy matrix aluminum (10-4A/cm2) improve the 1-2 order of magnitude；In the sodium hydroxide of 150g/L
Drop alkali-resistant property experiment in, it is anticorrosive up to 10min, and under equal conditions the anticorrosive time of Process on Aluminum Alloy Oxidation Film only have
Several seconds；The antibiotic property of coating is strong, in the experiment of steamed bread contact antibiotic property, the steamed bread of aluminium alloy matrix surface under equal ambient
The mildew in 24h, and the aluminium alloy that the present invention is processed can adhere to more than 72h, and 120 hours also will not going mouldy completely；Light
In solution methyl orange experiment, resolution ratio reaches more than 40% after 60min under sunlight, there is good photodissociation self-cleaning property.
Embodiment 3
The first step：After according to conventional aluminum alloys polishing rust-removal, washing, pickling degreasing, washing step, aluminium alloy is immersed
In the sulfuric acid solution of 100g/L, wherein the aluminum sulfate containing 20g/L, using needing the aluminium alloy of oxidation as anode, negative electrode is also
Aluminium alloy, reaction environment temperature is 20 DEG C, and using constant current source, electric current density is 50mA/cm2, oxidization time is 30min, is taken
The aluminium alloy gone out after oxidation is rinsed in the clear water of flowing, removes the electrolyte on oxide-film surface, and in aluminum alloy surface silver is obtained
The oxide-film of Lycoperdon polymorphum Vitt；
Second step：By the first step gained aluminium alloy as negative electrode, with graphite as anode, electrolyte be 25g/L silver nitrate,
5g/L magnesium sulfate and 25g/L sodium citrates, with nitre acid for adjusting pH to 0.5, the silver gray aluminium alloy after then the first step is aoxidized
Immersion carries out in the electrolytic solution electrolytic coloring, and cathode-current density is 40mA/cm2, the oxygen of redness is obtained after sedimentation time 300s
Change film.Then take out this aluminium alloy to rinse in the clear water of flowing, remove the electrolyte of residual；
3rd step：Titania gel is configured first：20mL butyl titanates are first added the dehydrated alcohol of 80ml, mixing is equal
It is even to obtain solution A；Ethanol of the 8ml glacial acetic acid with the 95% of 30ml is separately taken again is mixed to get B solution；Then A is poured slowly into into B
In, 30min is stirred rapidly, obtain titania gel.Then, the red aluminium alloy that second step is obtained is immersed in into titanium dioxide
20min in gel, in 80 DEG C of drying baker 30min is dried, and further takes out to cool down and rinsed well with clear water, drying, you can
Obtain titania gel sealing of hole film layer.
Red oxidization film tool color manufactured in the present embodiment is full, good decorative property, while having antibacterial, antibacterial, self-cleaning, dress
Decorations etc. are multi-functional.Wiped using reagent paper, just start for 3000 times to decolourize；Corrosion rate in 5% sodium chloride solution is 10-5-
10-6A/cm2, compared with alloy matrix aluminum (10-4A/cm2) improve the 1-2 order of magnitude；It is rotten in the drop alkali resistant of the sodium hydroxide of 150g/L
Corrosion experiment in, it is anticorrosive up to 5-6min, and under equal conditions the anticorrosive time of Process on Aluminum Alloy Oxidation Film there was only several seconds；Coating
Antibiotic property it is strong, in the experiment of steamed bread contact antibiotic property, the steamed bread of aluminium alloy matrix surface is long in 24h under equal ambient
It is mould, and the aluminium alloy that the present invention is processed can adhere to more than 72h, and 120 hours also will not going mouldy completely；Photodissociation methyl orange reality
In testing, resolution ratio reaches more than 75% after 60min under sunlight, there is good photodissociation self-cleaning property.
Claims (9)
1. the method for positive pole oxidation film on aluminum alloy surface hole being closed using titania gel, it is characterised in that：Including following steps
Suddenly：
The first step：Aluminum alloy surface electrolytic anodization
Using the one kind in aluminium alloy, graphite, rustless steel, lead, titanium alloy as negative electrode, made with the aluminium alloy for needing surface oxidation to protect
Anode carries out anodic oxidation, and in aluminum alloy surface porous oxide film is formed；
Second step：Surface-sealing
After the Process on Aluminum Alloy Oxidation Film surface water that the first step is obtained is rinsed well, it is placed in titania gel and soaks 20-
50min, takes out in 80-98 DEG C of drying；Titania gel sealing of hole film layer is obtained in aluminum alloy surface；
Titania gel preparation process is：Butyl titanate is added in dehydrated alcohol, mix homogeneously obtains solution A；Separately take again
Glacial acetic acid is mixed to get B solution with ethanol；Then A is poured slowly in B, is stirred, obtain titania gel；
Solution A is added in the dehydrated alcohol of 10-100ml by 5-30mL butyl titanates, and mix homogeneously is obtained；B solution is by 5-30ml
Glacial acetic acid is mixed to get with the ethanol that 10-100ml concentration expressed in percentage by volumes are 95%；After A is poured slowly in B, 30min is stirred, obtained
To titania gel.
2. the method that employing titania gel according to claim 1 closes positive pole oxidation film on aluminum alloy surface hole, its
It is characterised by：After first step aluminum alloy surface electrolytic oxidation, electrochemical coloring is carried out to aluminum alloy surface, then, carry out table
Face sealing of hole.
3. the method that employing titania gel according to claim 1 and 2 closes positive pole oxidation film on aluminum alloy surface hole,
It is characterized in that：The anode oxidation process is：
Anodic oxidation electrolyte is made up of sulphuric acid, aluminium ion, vitriolated mass-volume concentration in every liter of anodic oxidation electrolyte
For 120-180g/L, it is 5-20 g/L that aluminum ions mass-volume concentration is contained in every liter of anodic oxidation electrolyte；
The one kind of the aluminium ion in aluminum sulfate, meta-aluminate, aluminium hydroxide；
Oxidation current density is 40-60mA/cm2。
4. the method that employing titania gel according to claim 3 closes positive pole oxidation film on aluminum alloy surface hole, its
It is characterised by：10-40 DEG C of anodic oxidation electrolysis temperature, the electrolytic oxidation time is 20-40min.
5. the method that employing titania gel according to claim 2 closes positive pole oxidation film on aluminum alloy surface hole, its
It is characterised by：Aluminum alloy surface carries out the technological parameter of electrochemical coloring：
With graphite as anode, with the aluminium alloy after anodic oxidation as negative electrode,
Electrolysis temperature is 40-80 DEG C,
Electric current density is 5-100mA/cm2,
The pH value of electrolyte is controlled in 0.5-2,
Electrolyte is made up of coloring agent, complexant, solvent,
The mass-volume concentration containing coloring agent is 5-50g/L in every liter of solvent, and the mass-volume concentration containing complexant is 20-60g/
L。
6. the method that employing titania gel according to claim 5 closes positive pole oxidation film on aluminum alloy surface hole, its
It is characterised by：
The complexant is selected from tartaric acid, citric acid, pyrophosphoric acid, ethylenediaminetetraacetic acid, tartrate, citrate, pyrophosphoric acid
At least one in salt, edetate；
At least one of the coloring agent in argent, copper, the inorganic salt of zinc；The solvent is distilled water.
7. the method that employing titania gel according to claim 6 closes positive pole oxidation film on aluminum alloy surface hole, its
It is characterised by：The electrolysis time of electrochemical coloring is 30-300s.
8. the method that the employing titania gel according to claim 2 or 7 closes positive pole oxidation film on aluminum alloy surface hole,
It is characterized in that：The anode oxidation process adopts DC source with galvano-chemistry bepainting technique；The DC source is constant pressure
DC source or constant-current dc power supply.
9. the method that employing titania gel according to claim 1 closes positive pole oxidation film on aluminum alloy surface hole, its
It is characterised by：
The first step：After according to conventional aluminum alloys polishing rust-removal, washing, pickling degreasing, washing step, aluminium alloy is immersed into 180 g/
In the sulfuric acid solution of L, wherein the aluminum sulfate containing 10 g/L, using the aluminium alloy of oxidation is needed as anode, negative electrode is also aluminum conjunction
Gold, reaction environment temperature is 20 DEG C, and using constant current source, electric current density is 40 mA/cm2, oxidization time is 30min, takes out oxygen
Aluminium alloy after change is rinsed in the clear water of flowing, removes the electrolyte on oxide-film surface, and in aluminum alloy surface silver gray is obtained
Oxide-film；
Second step：By first step gained aluminium alloy as negative electrode, with graphite as anode, electrolyte is 10 g/L silver nitrate, 5 g/L
Magnesium sulfate and 10 g/L sodium citrates, with nitre acid for adjusting pH to 0.5, the silver gray aluminium alloy leaching after then the first step is aoxidized
Bubble carries out in the electrolytic solution electrolytic coloring, and cathode-current density is 60 mA/cm2, flavous oxygen is obtained after sedimentation time 90s
Change film；Then take out golden yellow aluminium alloy to rinse in the clear water of flowing, remove the electrolyte of residual；
3rd step：Titania gel is configured first：First 20mL butyl titanates are added the dehydrated alcohol of 70ml, mix homogeneously obtain
To solution A；8ml glacial acetic acid is separately taken again is mixed to get B solution with the ethanol that the mass-volume concentration of 35ml is 95%；Then A is delayed
Slowly pour in B, 30min is stirred rapidly, obtain titania gel；Then, the golden yellow aluminium alloy for second step being obtained is two
Soak in titanium oxide gel after 30min, take out, be dried in 90 DEG C of drying baker after 30min and be cooled to room temperature, rinsed with clear water
Totally, dry, you can obtain titania gel sealing of hole film layer.
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